The bottom-up design of polymer films exhibiting quadratic nonlinear optical properties that can be tuned optically and chemically is described. The polymer matrices are doped with metal-containing chromophores built around a Zn-II core and photoisomerizable ligands with two different geometries. These molecules possess specifically designed photophysical and nonlinear optical properties to be used towards all-optical poling, an interference process between one- and two-photon excitations that locally induces macroscopic second-order effects in polymer films. It is shown that grafting the molecules onto the polymer chains improves the stability of the macroscopic photoinduced nonlinearity in the films.